EP2892628A2 - Metal-organic frameworks - Google Patents
Metal-organic frameworksInfo
- Publication number
- EP2892628A2 EP2892628A2 EP13759305.9A EP13759305A EP2892628A2 EP 2892628 A2 EP2892628 A2 EP 2892628A2 EP 13759305 A EP13759305 A EP 13759305A EP 2892628 A2 EP2892628 A2 EP 2892628A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- compound
- alkyl
- group
- lig
- xylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/38—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving specific interaction not covered by one or more of groups B01D15/265 - B01D15/36
- B01D15/3804—Affinity chromatography
- B01D15/3828—Ligand exchange chromatography, e.g. complexation, chelation or metal interaction chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
- B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/33—Polycyclic acids
- C07C63/331—Polycyclic acids with all carboxyl groups bound to non-condensed rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/66—Polycyclic acids with unsaturation outside the aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
Definitions
- the present invention relates to certain compounds capable of forming metal-organic frameworks (MOFs), particularly MOFs which selectively sorb one component (e.g. para-xylene) from a mixture of components (e.g. m-/p-xylene mixture).
- MOFs metal-organic frameworks
- the invention also relates to methods of producing and using said compounds.
- o-xylene is used in making phthalic anhydride (PA); m-xylene for isophthalic acid; and p-xylene is used exclusively for making dimethyl terephthalate and terephthalic acid (DMT/TPA) which are raw materials used in the manufacture of polyethylene terephthalate (PET) used in polyester fibers, molded plastics, films, and blown beverage bottles 4 .
- PA phthalic anhydride
- m-xylene for isophthalic acid
- p-xylene is used exclusively for making dimethyl terephthalate and terephthalic acid (DMT/TPA) which are raw materials used in the manufacture of polyethylene terephthalate (PET) used in polyester fibers, molded plastics, films, and blown beverage bottles 4 .
- DMT/TPA dimethyl terephthalate and terephthalic acid
- Crystallisation-based processes exploit the large freezing point difference between p- xylene and the remaining components in the mixture.
- the recovery value of p-xylene is limited to the eutectic point, i.e. the temperature at which a second component starts to crystallize. Typical values for recovery are between 60-65 wt% for feed streams with about 20 wt% of p-xylene 6 .
- This limitation is one of the main drawbacks of crystallisation when processing feeds with a low concentration of p-xylene 7 .
- low temperature crystallisation methods have other serious drawbacks, including the large amount of energy required for cooling, and the heat- transfer problems that arise as solid p-xylene coats the inner walls of a cooled crystallisation vessel.
- An object of the present invention is to provide alternative compounds to serve as MOFs.
- a further object of the present invention is to provide alternative MOFs for purifying xylene mixtures.
- a further object of the present invention is to provide MOFs with improved sorption selectivity, especially with respect to xylene mixtures.
- a further object of the present invention is to provide an improved method of purifying mixtures, such as xylene mixtures.
- LIG polydentate ligand
- MOF metal organic framework
- LIG group is defined by Formula A (or a suitable ionised form thereof):
- n is an integer between 1 and 6 such that n individual and independently defined -L.R groups (i.e. L R ⁇ ... L n -R n ) are attached to CORE;
- CORE comprises one or more aromatic or heteroaromatic systems; each L group is the same or different, each being independently either absent or a linker selected from the group including (1 -3C)alkylene, (2-3C)alkenylene, (2- 3C)alkynylene, O, S, SO, S0 2 , N(R' a ), CO, CH(OR' a ), CON(R' a ), N(R' a )CO, N(R' a )CON(R' a ), S0 2 N(R' a ), N(R' a )S0 2 , OC(R' a ) 2 , SC(R' a ) 2 and N(R' a )C(R' b ) 2 , wherein R' a and R' are each independently hydrogen or (1 -8C)alkyl;
- each R group is the same or different, each being independently selected from an aryl or heteroaryl group bearing a lone pair of electrons capable of coordinating with M or substituted by a group bearing a lone pair of electrons capable of coordinating with M;
- CORE or any R group is optionally further substituted by one or groups selected from halogeno, trifluoromethyl, trifluoromethoxy, cyano, isocyano, nitro, hydroxy, mercapto, amino, formyl, carboxy (incl. carboxylic acid), carbamoyl, ureido, sulphonyl (incl. sulphonic acid), phosphoryl (incl. phosphonic acid), (1 -8C)alkyl, (2-8C)alkenyl, (2-
- a metal- organic framework comprising a compound of the first aspect.
- a sorbent material comprising the metal-organic framework (MOF) of the second aspect.
- a method of manufacturing a compound of the first aspect comprising associating an f-block metal ion (M) with a polydentate ligand (LIG), as defined herein, capable of co-ordinating with M to provide a metal organic framework (MOF) structure.
- M f-block metal ion
- LIG polydentate ligand
- a method of manufacturing an MOF of the second aspect comprising providing the compound of the first aspect in a solid form.
- a method of manufacturing a sorbent material of the third aspect comprising providing a MOF of the second aspect optionally in admixture with one or more auxiliary sorbent substances and/or one or more carrier substances.
- a method of selectively sorbing a desired component from a mixture of components comprising contacting the mixture of components with a sorbent material of the third aspect to selectively sorb the desired component within/to the sorbent material.
- a method of separating a desired component from a mixture of components comprising:
- a desired component from a mixture of components in accordance with the method of the seventh aspect to produce an sorption complex (i.e. comprising the desired component sorbed into/to the sorbent material);
- a purified product comprising (or consisting of) the desired component obtainable by, obtained by, or directly obtained by the method of the eighth aspect.
- a method of separating a p-xylene from a mixture of xylenes comprising:
- p-xylene obtainable by, obtained by, or directly obtained by the method of the eighth aspect.
- a desired component e.g. p-xylene
- a mixture of components e.g. mixture of xylenes
- a method of enriching a mixture initially comprising a desired component and a non-desired component, in the non-desired component (relative to the desired component), the method comprising:
- a desired component from the mixture by contacting the mixture with a sorbent material of the third aspect to selectively sorb the desired component within/to the sorbent material to produce a sorption complex (i.e. comprising the desired component sorbed into/to the sorbent material) and an non-desired- component-enriched mixture; ii) separating the non-desired-component-enriched mixture from the sorption complex; iii) optionally repeating step i) upon the non-desired-component-enriched mixture of step ii);
- a fourteenth aspect of the present invention there is provided a purified product comprising (or consisting of) the non-desired component obtainable by, obtained by, or directly obtained by the method of the thirteenth aspect.
- a method of separating a m-xylene from a mixture of xylenes comprising p-xylene and m-xylene comprising:
- step iii) optionally repeating step i) upon the m-xylene-enriched mixture of step ii);
- m-xylene obtainable by, obtained by, or directly obtained by the method of the fifteenth aspect.
- Figure 1 shows two optical microscope images of Compound 1 at 1 1 .25x magnification.
- Figure 2 shows four SEM images of a crystal of Compound 1.
- Figure 4 shows a TGA profile of compound 1.
- Figure 6 shows (a) an N 2 isotherm of compound 2 collected at 77 K; and (b) an H 2 0 isotherm of compound 2 collected at 295 K following activation 1 at 100 °C at 10 "5 mbar overnight.
- Figure 7 shows (a) a C0 2 isotherm of compound 2 collected at 195 K following activation 1 at 1 00 °C at 1 0 "5 mbar overnight; (b) a BET plot for surface area determination; and (c) a Dubnin-Raduschevich plot for calculation of pore volume based on 1 95 K isotherm.
- Figure 8 relates to Isosteric Heat (Q st ) Determination of compound 2 and shows (a) C0 2 and CH 4 isotherms collected at 273 K and 298 K; and (b) C0 2 and CH 4 Q st .
- Figure 9 shows TGA profiles of loaded 2 with pX and mX individually.
- Figure 1 0 shows (a) Powder x-ray diffraction profiles of loaded material following xylene uptake experiments on compound 2; and (b) TGA profiles of loaded material following xylene uptake experiments on compound 2.
- Figure 1 1 shows analysis of the relative amounts of compound 2 (red) and xylene loaded compound 2PM (blue) over the time course of the pXmX selectivity experiments.
- Figure 12 shows selectivity a pXmX of 2 with increasing pX uptake.
- MOF metal-organic framework
- MOFs of the present invention form porous structures.
- MOFs of the invention are 3-dimensional structures.
- sorb refers to the process of sorption of certain compounds (sorbates) within/to the pores of a particular solid structure (sorbent), such as where an "sorbent material” sorbs a desired component from a component mixture.
- sorbent solid structure
- sorbent encompass “absorb”, “absorption” “absorbent”, and “absorbate”, where sorbates are sorbed within the bulk of a sorbent.
- sorb also encompasses “adsorb”, “adsorption”, “adsorbent”, and “adsorbate” where sorbates are sorbed to the surface of a sorbent.
- sorption means “absorption”.
- sorption means "adsorption”.
- selective sorb refers to a process in which a sorbent (i.e. porous solid material) uptakes one sorbate in preference to other components or potential sorbates which are a part of the same original mixture.
- a sorbent i.e. porous solid material
- mixture of components generally refers to a mixture of different compounds from which one particular component is to be preferentially separated, e.g. through sorption into/to a sorbent material.
- the term "desired component” refers to a particular component of a mixture intended for selective extraction.
- f-block metal ion is a term of art which refers to the ionised form of a metal residing in the "f-block" of the periodic table of elements.
- the f-block consists of lanthanides (La-Yb) and actinides (Ac-No), and ions of all such metals are encompassed by the term "f-block metal ion”.
- polydentate ligand refers to ligands comprising two or more atoms capable of binding a central f-block metal ion in a coordination complex. This is in contrast to monodentate ligands where only one atom can coordinate (e.g. as per solvents such as H 2 0 or EtOH).
- alkyl includes both straight and branched chain alkyl groups. References to individual alkyl groups such as “propyl” are specific for the straight chain version only and references to individual branched chain alkyl groups such as “isopropyl” are specific for the branched chain version only.
- (1 -6C)alkyl includes (1 -4C)alkyl, (1 - 3C)alkyl, propyl, isopropyl and t-butyl.
- phenyl(1 -6C)alkyl includes phenyl(1 -4C)alkyl, benzyl, 1 -phenylethyl and 2-phenylethyl.
- (m-nC) or "(m-nC) group” used alone or as a prefix, refers to any group having m to n carbon atoms.
- alkylene is an alkyl, alkenyl, or alkynyl group that is positioned between and serves to connect two other chemical groups.
- (1 - 6C)alkylene means a linear saturated divalent hydrocarbon radical of one to six carbon atoms or a branched saturated divalent hydrocarbon radical of three to six carbon atoms, for example, methylene, ethylene, propylene, 2-methylpropylene, pentylene, and the like.
- (2-6C)alkenylene means a linear divalent hydrocarbon radical of two to six carbon atoms or a branched divalent hydrocarbon radical of three to six carbon atoms, containing at least one double bond, for example, as in ethenylene, 2,4-pentadienylene, and the like.
- (2-6C)alkynylene means a linear divalent hydrocarbon radical of two to six carbon atoms or a branched divalent hydrocarbon radical of three to six carbon atoms, containing at least one triple bond, for example, as in ethynylene, propynylene, and butynylene and the like.
- (3-8C)cycloalkyl means a hydrocarbon ring containing from 3 to 8 carbon atoms, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or bicyclo[2.2.1 ]heptyl.
- (3-8C)cycloalkenyl means a hydrocarbon ring containing at least one double bond, for example, cyclobutenyl, cyclopentenyl, cyclohexenyl or cycloheptenyl, such as 3-cyclohexen-1 - yl, or cyclooctenyl.
- (3-8C)cycloalkyl-(1 -6C)alkylene means a (3-8C)cycloalkyl group covalently attached to a (1 -6C)alkylene group, both of which are defined herein.
- halo or halogeno refers to fluoro, chloro, bromo and iodo.
- heterocyclyl means a non-aromatic saturated or partially saturated monocyclic, fused, bridged, or spiro bicyclic heterocyclic ring system(s).
- heterocyclyl includes both monovalent species and divalent species.
- Monocyclic heterocyclic rings contain from about 3 to 12 (suitably from 3 to 7) ring atoms, with from 1 to 5 (suitably 1 , 2 or 3) heteroatoms selected from nitrogen, oxygen or sulfur in the ring.
- Bicyclic heterocycles contain from 7 to 17 member atoms, suitably 7 to 12 member atoms, in the ring.
- Bicyclic heterocycles contain from about 7 to about 17 ring atoms, suitably from 7 to 12 ring atoms. Bicyclic heterocyclic(s) rings may be fused, spiro, or bridged ring systems.
- heterocyclic groups include cyclic ethers such as oxiranyl, oxetanyl, tetrahydrofuranyl, dioxanyl, and substituted cyclic ethers.
- Heterocycles containing nitrogen include, for example, azetidinyl, pyrrolidinyl, piperidinyl, piperazinyl, tetrahydrotriazinyl, tetrahydropyrazolyl, and the like.
- Typical sulfur containing heterocycles include tetrahydrothienyl, dihydro-1 ,3-dithiol, tetrahydro-2H- thiopyran, and hexahydrothiepine.
- Other heterocycles include dihydro-oxathiolyl, tetrahydro-oxazolyl, tetrahydro-oxadiazolyl, tetrahydrodioxazolyl, tetrahydro-oxathiazolyl, hexahydrotriazinyl, tetrahydro-oxazinyl, morpholinyl, thiomorpholinyl, tetrahydropyrimidinyl, dioxolinyl, octahydrobenzofuranyl, octahydrobenzimidazolyl, and octahydrobenzothiazolyl.
- the oxidized sulfur heterocycles containing SO or S02 groups are also included.
- examples include the sulfoxide and sulfone forms of tetrahydrothienyl and thiomorpholinyl such as tetrahydrothiene 1 ,1 -dioxide and thiomorpholinyl 1 ,1 -dioxide.
- heterocyclyl groups are saturated monocyclic 3 to 7 membered heterocyclyls containing 1 , 2 or 3 heteroatoms selected from nitrogen, oxygen or sulfur, for example azetidinyl, tetrahydrofuranyl, tetrahydropyranyl, pyrrolidinyl, morpholinyl, tetrahydrothienyl, tetrahydrothienyl 1 ,1 -dioxide, thiomorpholinyl, thiomorpholinyl 1 ,1 -dioxide, piperidinyl, homopiperidinyl, piperazinyl or homopiperazinyl.
- any heterocycle may be linked to another group via any suitable atom, such as via a carbon or nitrogen atom.
- reference herein to piperidino or morpholino refers to a piperidin-1 -yl or morpholin-4-yl ring that is linked via the ring nitrogen.
- bridged ring systems is meant ring systems in which two rings share more than two atoms, see for example Advanced Organic Chemistry, by Jerry March, 4th Edition, Wiley Interscience, pages 131 -133, 1992.
- bridged heterocyclyl ring systems include, aza- bicyclo[2.2.1 ]heptane, 2-oxa-5-azabicyclo[2.2.1 ]heptane, aza-bicyclo[2.2.2]octane, aza- bicyclo[3.2.1 ]octane and quinuclidine.
- Heterocyclyl(1 -6C)alkyl means a heterocyclyl group covalently attached to a (1 - 6C)alkylene group, both of which are defined herein.
- heteroaryl or “heteroaromatic” means an aromatic mono-, bi-, or polycyclic ring incorporating one or more (for example 1 -4, particularly 1 , 2 or 3) heteroatoms selected from nitrogen, oxygen or sulfur.
- heteroaryl includes both monovalent species and divalent species. Examples of heteroaryl groups are monocyclic and bicyclic groups containing from five to twelve ring members, and more usually from five to ten ring members.
- the heteroaryl group can be, for example, a 5- or 6-membered monocyclic ring or a 9- or 10- membered bicyclic ring, for example a bicyclic structure formed from fused five and six membered rings or two fused six membered rings.
- Each ring may contain up to about four heteroatoms typically selected from nitrogen, sulfur and oxygen.
- the heteroaryl ring will contain up to 3 heteroatoms, more usually up to 2, for example a single heteroatom.
- the heteroaryl ring contains at least one ring nitrogen atom.
- the nitrogen atoms in the heteroaryl rings can be basic, as in the case of an imidazole or pyridine, or essentially non-basic as in the case of an indole or pyrrole nitrogen. In general the number of basic nitrogen atoms present in the heteroaryl group, including any amino group substituents of the ring, will be less than five.
- heteroaryl examples include furyl, pyrrolyl, thienyl, oxazolyl, isoxazolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1 ,3,5-triazenyl, benzofuranyl, indolyl, isoindolyl, benzothienyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzothiazolyl, indazolyl, purinyl, benzofurazanyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, cinnolinyl, pteridinyl, naphthy
- Heteroaryl also covers partially aromatic bi- or polycyclic ring systems wherein at least one ring is an aromatic ring and one or more of the other ring(s) is a non-aromatic, saturated or partially saturated ring, provided at least one ring contains one or more heteroatoms selected from nitrogen, oxygen or sulfur.
- partially aromatic heteroaryl groups include for example, tetrahydroisoquinolinyl, tetrahydroquinolinyl, 2-oxo-1 ,2,3,4-tetrahydroquinolinyl, dihydrobenzthienyl, dihydrobenzfuranyl, 2,3-dihydro-benzo[1 ,4]dioxinyl, benzo[1 ,3]dioxolyl, 2,2- dioxo-1 ,3-dihydro-2-benzothienyl, 4,5,6,7-tetrahydrobenzofuranyl, indolinyl,
- heteroaryl groups examples include but are not limited to pyrrolyl, furanyl, thienyl, imidazolyl, furazanyl, oxazolyl, oxadiazolyl, oxatriazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, triazolyl and tetrazolyl groups.
- heteroaryl groups examples include but are not limited to pyridyl, pyrazinyl, pyridazinyl, pyrimidinyl and triazinyl.
- a bicyclic heteroaryl group may be, for example, a group selected from:
- bicyclic heteroaryl groups containing a six membered ring fused to a five membered ring include but are not limited to benzfuranyl, benzthiophenyl, benzimidazolyl, benzoxazolyl, benzisoxazolyl, benzthiazolyl, benzisothiazolyl, isobenzofuranyl, indolyl, isoindolyl, indolizinyl, indolinyl, isoindolinyl, purinyl (e.g., adeninyl, guaninyl), indazolyl, benzodioxolyl and pyrazolopyridinyl groups.
- bicyclic heteroaryl groups containing two fused six membered rings include but are not limited to quinolinyl, isoquinolinyl, chromanyl, thiochromanyl, chromenyl, isochromenyl, chromanyl, isochromanyl, benzodioxanyl, quinolizinyl, benzoxazinyl, benzodiazinyl, pyridopyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, phthalazinyl, naphthyridinyl and pteridinyl groups.
- Heteroaryl(1 -6C)alkyl means a heteroaryl group covalently attached to a (1 - 6C)alkylene group, both of which are defined herein.
- heteroaralkyl groups include pyridin-3-ylmethyl, 3-(benzofuran-2-yl)propyl, and the like.
- aryl or "aromatic” means a cyclic or polycyclic aromatic ring having from 5 to 16 carbon atoms.
- aryl includes both monovalent species and divalent species. Examples of aryl groups include, but are not limited to, phenyl, biphenyl, naphthyl and the like. In particular embodiment, an aryl is phenyl.
- aryl(1 -6C)alkyl means an aryl group covalently attached to a (1 - 6C)alkylene group, both of which are defined herein.
- aryl-(1 -6C)alkyl groups include benzyl, phenylethyl, and the like
- heterocyclyl(m-nC)alkyl comprises (m-nC)alkyl substituted by heterocyclyl.
- a compound of the invention means those compounds which are disclosed herein, both generically and specifically. Such compounds may include acceptable salts or solvates thereof.
- a compound defined by a formula suitably includes compounds comprising species or units of said formula, optionally in association with further species or units.
- said formula defines the compound precisely, such that said compound consists of species or units of said formula (i.e. where said compound is substantially free of further species or units).
- the present invention provides a new class of MOFs for selectively extracting and separating particular desired components from mixtures. These MOFs are particularly effective at selectively extracting/separating p-xylene from xylene mixtures, though the inherent flexibility of the MOFs of the invention widens the scope of their applicability.
- a MOF of the invention By contacting a MOF of the invention (or sorbent materials formed therefrom) with a liquid mixture, one or more components (preferably one) will be selectively extracted over others in the mixture.
- This process yields a solid-phase sorption complex comprising the MOF and the extracted component(s), and also "mother liquors" enriched in the remaining non-extracted components.
- the solid-phase sorption complex can then be separated from the mother liquors before then treating the sorption complex to recover the sorbed component(s) (i.e. sorbates) from the MOF (i.e. sorbent). In this manner, a desired component can be separated from a mixture, whilst the mixture is itself enriched in any remaining components.
- MOFs of the invention are considered effective without the need for multiple sorption/separation cycles, it is envisaged that established "simulated moving bed” technology 1 1 ' 12 known in the art could be employed to make optimum use of the MOFs of the invention.
- the MOFs of the present invention offer excellent sorption selectivity, especially with respect to the selective sorption of p-xylene from xylene mixtures.
- MOFs of the present invention generally outperform MOFs and Zeolites of the prior art in terms of substrate sorption selectivity.
- a further advantage of MOFs of the present invention is that they remain efficient and selective over a range of solvation states.
- a further advantage of MOFs of the present invention is that they permit liquid phase extractions, particularly with respect to xylenes, thus avoiding problematic handling of solid phase components.
- MOFs of the present invention allow for straightforward recovery of substrates sorbed therein/thereto.
- MOFs of the present invention can generally be successively re-used in sorption/extraction processes.
- the MOFs of the present invention are highly stable on storage, and can withstand aggressive manufacturing conditions, such as high-temperature drying steps. Moreover, the MOFs of the present invention are substantially stable in the presence of moisture and liquid water, which can be crucial in their practical applications.
- MOF structures of the present invention are highly flexible. Without wishing to be found by any particular theory, it appears that the MOFs of the present invention change structure as a desired component is sorbed thereinto/thereto. It is thought that the greater selectivity afforded by MOFs of the present invention is at least in part due to this inherent flexibility, which seemingly allows the MOFs to adopt lower energy structural configurations as they selectively sorb the desired component. This additional energetic factor may account for the increased discrimination for particular components over others in a mixture.
- MOFs exhibiting such surprising levels of structural flexibility significantly widens the scope of compound mixtures which may be purified using MOFs. For instance, by varying the ligand and/or metal ion, the MOF can be tuned to selectively sorb a range of different substrates from various different mixtures. As such, the class of MOFs of the present invention are more widely applicable and customisable than any MOFs previously discovered.
- M and LIG are suitably respectively present in the compound in a molar ratio of x : y.
- x and y suitably respectively indicate the relative stoichiometries of M and LIG within the compound, both x and y being greater than zero.
- the compounds of the present invention are suitably MOF-compounds, i.e. capable of adopting an MOF structure in a crystalline form.
- the crystal structure of the MOF-compounds of the invention is readily determined by methods known in the art such as crystallography.
- the present invention provides an MOF-compound defined by Formula I:
- M is an f-block metal ion
- LIG is a polydentate ligand as defined herein;
- x and y indicate the relative stoichiometries of M and LIG respectively, both x and y being greater than zero;
- the compounds of the invention essentially comprise a metal-ligand complex.
- the polydentate ligands (LIG) are co-ordinated to some or all of the metal ions (M) present in the complex.
- the MOF-compound comprises a complex in which the f-block metal ion has a co-ordination number of at least 6, suitably 9 (as discernable by crystallography).
- the co-ordination denticity may vary for each metal-ligand combination, and individual ligands may in some cases bridge between metal ions.
- the metal-ligand complex is suitably neutral.
- metal ions (M) and polydentate ligand (LIG) suitably constitute the majority (i.e. over 50%) of the molecular weight of the MOF-compounds
- other species such as solvates and/or auxiliary counterions (whether counterions to the metal ions or counterions to the ligand), may also be present in the complexes.
- the MOF-compound may be provided as a salt thereof.
- the MOF-compound may be provided as a salt with an appropriate anion (e.g. a halide).
- the MOF-compound may be provided as a salt with an appropriate cation (e.g. a metal ion, whether an f-block metal or otherwise).
- the MOF-compound is (substantially) neutral, i.e. the ligand charges balance with the metal ion charges.
- the respective oxidation (or ionisation) states of M and LIG are of (substantially) equal magnitude but opposite polarity, most suitably 3+ and 3- respectively.
- x and y may be substantially equal and the metal-ligand complex substantially neutral.
- the MOF-compound may be provided as a solvate thereof.
- the solvate suitably includes solvent molecules co-ordinated directly to the metal ions (M).
- the MOF-compound may be (substantially) free of solvate.
- solvates may affect the structure of the MOFs, but will not generally affect the relative stoichiometry between the metal ions (M) and the polydentate ligands (LIG), assuming said solvate is uncharged.
- auxiliary counterions e.g. halides, such as chloride
- M metal ions
- LIG polydentate ligands
- auxiliary counterions may be those present in the original species used to form the MOF-compounds.
- the relative stoichiometry of the metal ion (M) to polydentate ligand (LIG) depends on a number of factors, including the relative amounts of metal ions and polydentate ligand used to form the MOF-compounds, the oxidation state of the metal ions, the ionisation state of the ligand, the presence of auxiliary counterions, the presence of solvates.
- M and LIG are suitably respectively present in the compound in a molar ratio of x : y.
- the compound may be said to comprise species defined by the formula [M] x [LIG] y , where x and y respectively indicate the relative stoichiometries of M and LIG within the compound, both x and y being greater than zero.
- the MOF-compound may be polydentate ligand-deficient, i.e. so that the co-ordination spheres of the metal ions are unsaturated with respect to the ligand.
- the MOF-compound may be over-saturated with polydentate ligand, for instance, such that more ligands are involved in bridging between the metal ions.
- the MOF-compounds are somewhere between these two extremes.
- the proportions of metal ions to ligand may affect the structure and/or pore sizes of the MOFs formed from the MOF-compounds.
- the ratio of metal ion (M) to polydentate ligand (LIG) is expressed as x:y or x/y.
- this ratio which reflects the relative stoichiometry between the metal ions (M) and polydentate ligand (LIG), may vary depending on a number of factors, and may in some embodiments be predetermined for optimum effect.
- the ratio x:y is between 10:1 and 1 :10, suitably between 5:1 and 1 :5, more suitably between 2:1 and 1 :2, and most suitably substantially 1 :1 .
- the x/y ratio is such that the total charge of metal ions is at least 70% neutralised by the total charge of the polydentate ligand, more suitably at least 90% neutralised, most suitably at least 95% neutralised. Any charge on the metal ions not neutralised by the polydentate ligand is suitably neutralised by auxiliary ligands or counterions. In a particular embodiment, the total charge of the metal ions is (substantially) 100% neutralised by the charge of the polydentate ligand.
- the MOF-compounds of the invention comprise a plurality of different ligands and/or auxiliary counterions.
- the MOF-compound may comprise multiple different polydentate ligands, as defined herein.
- the LIG group may in fact consist of multiple different LIG groups each independently defined as herein described in relation to the LIG group.
- the LIG group may be represented as [LIG 1 ] y1 [LIG2]y2.. -[LIG n ] yn such that the MOF-compound is defined by the
- the MOF-compound may comprise other auxiliary ligands, such as monodentate ligands and the like. In this manner, the MOF-complex may be considered "doped", so as to affect the structure and/or pore sizes to provide the optimal MOF for a given circumstance.
- the MOF-compounds of the invention may also comprise a plurality of different metal ions, so long as at least one f-block metal ion (M) is present.
- M f-block metal ion
- at least 10 wt% of the total metal ions present in the MOF-compound are f-block metal ions, suitably at least 50 wt%, more suitably at least 90 wt%, most suitably at least 95 wt%.
- all of the metal ions present in the MOF-compound are f-block metal ions.
- M is an f-block metal ion, i.e. from the "f-block" of the periodic table of elements.
- the f-block metal ion (M) is a lanthanide metal ion.
- the f-block metal ion is suitably selected from a lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, or yttrium ion.
- the f-block metal ion is selected from a lanthanum, cerium, praseodymium, neodymium, samarium, or europium ion. In a particular embodiment the f-block metal ion is selected from a lanthanum, cerium, praseodymium, neodymium, or samarium ion. In a particular embodiment, the f-block metal ion is a cerium ion.
- the f-block metal ion is selected from a lanthanum, cerium, praseodymium, neodymium or samarium ion In a particular embodiment, the f-block metal ion is neodymium.
- the f-block metal ion is suitably cationic, and suitably has an oxidation state of 2+, 3+, or 4+. In a particular embodiment, the f-block metal ion is in the 3+ oxidation state.
- the f-block metal ion is cerium (III) - i.e. Ce 3+ .
- the f-block metal ion is neodymium (III) - i.e. Nd 3+ .
- LIG polydentate ligand
- M metal organic framework
- LIG comprises co-ordinating functionalities, i.e. functional groups with a lone pair of electrons capable of coordinating with M.
- the LIG group may include a plurality of different LIG groups.
- LIG may be represented as [LIGi] y i [LIG 2 ]y2- - -[LIGn]yn.
- each LIG group is defined by Formula A (or a suitable ionised form thereof):
- n is an integer between 1 and 6 such that n individual and independently defined -L.R groups (i.e. L R ⁇ ... L n -R n ) are attached to CORE;
- CORE comprises one or more aromatic or heteroaromatic systems;
- each L group is the same or different, each being independently either absent or a linker selected from the group including (1 -3C)alkylene, (2-3C)alkenylene, (2- 3C)alkynylene, O, S, SO, S0 2 , N(R' a ), CO, CH(OR' a ), CON(R' a ), N(R' a )CO, N(R' a )CON(R' a ), S0 2 N(R' a ), N(R' a )S0 2 , OC(R' a ) 2 , SC(R' a ) 2 and N(R' a )C(R' b ) 2 , wherein R' a and R' are each independently hydrogen or (1 -8C)alkyl;
- each R group is the same or different, each being independently selected from an aryl or heteroaryl group bearing a lone pair of electrons capable of coordinating with M or substituted by a group bearing a lone pair of electrons capable of coordinating with M;
- CORE or any R group is optionally further substituted by one or groups selected from halogeno, trifluoromethyl, trifluoromethoxy, cyano, isocyano, nitro, hydroxy, mercapto, amino, formyl, carboxy (incl. carboxylic acid), carbamoyl, ureido, sulphonyl (incl. sulphonic acid), phosphoryl (incl.
- A/-(1 -6C)alkylsulphamoyl A/,A/-di-[(1 -6C)alkyl]sulphamoyl, (1 -6C)alkanesulphonylamino and ⁇ /-(1 - 6C)alkyl-(1 -6C)alkanesulphonylamino.
- LIG group may suitably encompass any acceptable ionised forms thereof.
- references to LIG group substituents such as carboxylic acids may also include its conjugate base, i.e. a carboxylate anion.
- the polydentate ligand suitably complexes directly with the f-block metal ion (i.e. within the inner co-ordination sphere).
- the polydentate ligand may be a neutral species, for instance, where auxiliary counterions serve to neutralise the charge of the f-block metal ions.
- LIG comprises one or more ionised groups to thereby provide one or more anions. Such anions may then serve as counterions to the f-block metal ions as well as well as coordinating groups within the metal-ligand complex.
- LIG comprises one or more ionised groups characterised as the conjugate base of an acid (e.g. carboxylate groups).
- LIG comprises either or both ionised and/or ionisable groups (e.g. carboxylate and carboxylic acid groups).
- the ratio of ionised to ionisable groups can be selectively varied, for instance, by varying pH.
- the ratio of ionised to ionisable groups within LIG may be adapted so as to provide a (substantially) neutral metal-ligand complex.
- LIG may comprise 4 co-ordinating groups, 3 of which are ionised (e.g. carboxylate) and 1 of which is a non-ionised ionisable group (e.g. carboxylic acid) so as to give an overall 3- charge capable of neutralising a 3+ charge on the f-block metal ion.
- LIG comprises 4 or more ionised and/or ionisable groups.
- LIG comprises 4 or more carboxylic and/or carboxylate groups.
- LIG comprises 4 carboxylic and/or carboxylate groups.
- the CORE group of the ligand suitable has n individual and independently defined -L.R groups attached directly to appropriate position(s) of the aromatic and/or heteroaromatic systems, preferably at different positions where n is greater than 1 .
- the -L-R groups are juxtaposed around the CORE group to enable polydentate co-ordination with M, and optionally also bridging between M units.
- LIG groups suitable in the MOF-compounds of the invention include, for example, compounds of the formula A, or suitably ionised forms thereof, wherein, unless otherwise stated, each of CORE, n, L groups, and R groups has any of the meanings defined hereinbefore or in any of paragraphs (1 ) to (23) hereinafter:-
- n is an integer between 2 and 4.
- n is 4 such that 4 individual and independently defined -L.R groups (i.e. L ⁇ R ⁇ L 2 -R 2 , L 3 - R 3 , L4-R4) are attached to CORE.
- CORE comprises one or more aromatic systems, optionally substituted as herein defined.
- CORE is a benzene ring, optionally substituted as herein defined.
- CORE is a benzene ring and n is 4 such that the benzene ring is substituted in the 1 , 2, 4, and 5- positions with 4 -L.R groups (i.e. L ⁇ R ⁇ L 2 -R 2 , L 3 -R 3 , L 4 -R 4 ) as herein defined, wherein the benzene ring is optionally further substituted as herein defined.
- each L group is the same or different, each being independently either absent or a (2- 3C)alkynylene linker.
- each R group is the same or different, each being independently selected from an aryl group substituted by a group bearing a lone pair of electrons capable of coordinating with M, wherein each R group is optionally further substituted as herein defined.
- each R group is the same.
- each R group is aryl substituted by a group bearing a lone pair of electrons capable of coordinating with M selected from :
- each R group is optionally further substituted as herein defined.
- Each R group is defined by:
- each R group is aryl substituted by a carboxy (incl. carboxylic acid) group, wherein each R group is optionally further substituted as herein defined.
- each R group is aryl substituted by a carboxylate or carboxylic acid group, wherein each R group is optionally further substituted as herein defined.
- CORE or any R group is optionally further substituted by one or more groups selected from halogeno, cyano, amino, carboxy (incl. carboxylic acid), carbamoyl, (1 -8C)alkyl, (1 - 8C)alkoxy,
- CORE or any R group is optionally further substituted by one or more groups selected from halogeno, cyano, amino, carboxy (incl. carboxylic acid), carbamoyl, (1 -4C)alkyl, (1 - 4C)alkoxy,
- CORE or any R group is optionally further substituted by one or more groups selected from halogeno, cyano, amino, carboxy (incl. carboxylic acid), (1 -4C)alkyl, (1 -4C)alkoxy, (1 -4C)alkylsulphonyl, (1 -4C)alkylamino, di-[(1 -4C)alkyl]amino, (1 -4C)alkoxycarbonyl, (2-4C)alkanoylamino.
- CORE or any R group is optionally further substituted by one or more groups selected from fluoro, chloro, bromo, iodo, methyl, (1 -8C)alkyl, amino, (1 -8C)alkylamino, di-[(1 - 8C)alkyl]amino, (2-8C)alkanoylamino, carboxy (incl. carboxylic acid, carboxylate, or carboxy ester), hydroxyl, (1 -8C)alkoxy, (1 -4C)alkylsulphonyl, or cyano.
- R groups may themselves be a group (as defined herein) bearing a lone pair of electrons capable of coordinating with M.
- the LIG group is defined by Formula B (or a suitable ionised form thereof), optionally further substituted as defined herein:
- the LIG group is defined by Formula C (or a suitable ionised form thereof), optionally further substituted as defined herein:
- R groups (R R 2 , R 3 , R ) are as defined herein.
- the LIG group is defined by Formula D (or a suitable ionised form thereof), optionally further substituted as defined herein:
- L 1 : L 2 , L 3 , and L 4 are each independently defined as herein, and wherein at least one of Z Z 2 , Z 3 , Z 4 , and Z 5 is a group bearing a lone pair of electrons capable of coordinating with M as defined herein, whilst the others of Z Z 2 , Z 3 , Z 4 , and Z 5 are each independently hydrogen or any optional substituent defined herein in relation to R group.
- ⁇ and Z 5 are hydrogen.
- Z Z 3 , and Z 5 are hydrogen whilst Z 2 and Z 4 are groups other than hydrogen as defined herein (most suitably both are carboxylate or carboxylic acid groups).
- Z Z 2 , Z 4 , and Z 5 are hydrogen whilst Z 3 is a group other than hydrogen as defined herein (most suitably a carboxylate or a carboxylic acid group).
- the LIG group is defined by Formula E (or a suitable ionised form thereof), optionally further substituted as defined herein:
- Z Z 2 , Z 3 , Z 4 , and Z 5 is a group bearing a lone pair of electrons capable of coordinating with M as defined herein, whilst the others of Z Z 2 , Z 3 , Z 4 , and Z 5 are each independently hydrogen or any optional substituent defined herein in relation to R group.
- ⁇ and Z 5 are hydrogen.
- Z Z 3 , and Z 5 are hydrogen whilst Z 2 and Z 4 are groups other than hydrogen as defined herein (most suitably both are carboxylate or carboxylic acid groups).
- Z Z 2 , Z 4 , and Z 5 are hydrogen whilst Z 3 is a group other than hydrogen as defined herein (most suitably a carboxylate or a carboxylic acid group).
- the LIG group is selected from any one of (or a suitable ionised form of):
- the LIG group is (or a suitable ionised form of):
- LIG groups are known as 4',5'-bis(4- carboxyphenyl)-[1 ,1 ':2',1 "-terphenyl]-4,4"-dicarboxylic acids, and are otherwise known in the art as tetrakis(4-carboxyphenyl)benzene (H 4 TCPB or HTCPB).
- the LIG roup is:
- the MOF-compounds may comprise one or more solvates.
- Solvates may include any suitable solvating molecules, though most typically one or more of the solvate has a lone pair of electrons capable of co-ordinating with M.
- the solvates typically comprise a hetero atom, such as nitrogen or oxygen.
- the solvates are protic solvents, such as water or alcohols.
- the solvates are water and/or ethanol.
- the solvates are both water and ethanol.
- Typical solvates include [M] x [LIG] y (EtOH) a (H 2 0) b , where x and y are between 0.1 and 1 , a is a number between 0 and 0.5 (suitably 0.1 and 0.3) and b is a number between 0 and 3 (suitably between 1 and 2.8)ln a particular embodiment, especially where M is cerium(lll), LIG is HTCPB, and x and y are substantially equal to 1 , the solvate is either [M] x [LIG] y (H 2 0) 2 . 75 (EtOH)o. 28 , [M] x [LIG] y .or [M] x [LIG] y (H 2 0) 1 . 8 .
- the MOF-compound comprises less than 20 wt% solvate(s), suitably less than 10 wt%, suitably less than 5 wt%, suitably less than 2 wt%. In a particular embodiment, the MOF-compound is (substantially) free of solvate(s).
- the solvation state typically affects the 3-dimensional structure of the MOF, particularly the pore sizes and/or the size and/or shape of channels to the pores.
- the less solvate present in the MOF or MOF-compound the more selectively the MOF can sorb p- xylene from a mixture of xylenes.
- MOFs of the present invention may be tuned appropriately.
- MOFs Metal-Organic Frameworks
- the present invention provides a metal-organic framework (MOF) comprising a compound as defined herein.
- MOF metal-organic framework
- the MOF per se generally relates to the isolated solid form the MOF-compound.
- MOFs of the present invention are generally porous, and suitably comprise pores and/or channels into which or through which substrates may be sorbed (whether absorbed or adsorbed).
- the class of MOFs of the present invention are particularly effective at selectively sorbing one component from a component mixture, especially p-xylene from a mixture of xylenes. This is due to the favourable pore/channel structure exhibited, which allows for discrimination between components of a mixture.
- references herein to an MOF per se relates to the isolated solid form the MOF-compound, features described herein in relation to the MOF-compound (e.g. solvates and solvate content) may equally apply to the MOF per se.
- the MOF is (substantially) free of solvates.
- the MOF is a porous material in which at least some of the pores are accessible to the xylenes (i.e. not occupied by other guests). This is generally the "active" form of the MOF.
- the MOFs of the present invention are substantially physically composed of porous crystalline material, and substantially free of amorphous and/or non-porous material.
- the physical 3-D structure is suitably determined by powder X-ray diffraction and/or scanning electron microscopy.
- the MOFs are suitably composed of porous crystalline material within the limits of these techniques, i.e. >99%.
- MOFs of the present invention are suitably provided in crystalline form, suitably as a powder.
- the present invention provides a sorbent material comprising the metal-organic framework (MOF) as defined herein.
- MOF metal-organic framework
- the sorbent material may be absorbant, adsorbent, or both.
- the sorbent material is absorbent.
- the sorbent material may be provided in a variety of solid physical forms. Most suitably the sorbent material is provided as a powder, most suitably a crystalline powder. The sorbent material is suitably provided as a mobile solid form, for instance, so that it may be used in association with "simulated moving bed” technology.
- the sorbent material may comprise the MOF of the invention in admixture with one or more further MOFs of the present invention and/or one or more auxiliary sorbent substances and optionally one or more carrier substances.
- Further MOFs may include other MOFs falling within the scope of the invention, or other MOFs of the prior art.
- Auxiliary sorbent substances may include a range of substances known in the art, such as zeolites.
- MOFs or auxiliary sorbent substances may increase selectivity or the overall efficiency of the sorption process.
- any carrier substances used within the sorbent materials are inert, at least in relation to the mixtures upon which the sorbent materials are intended to be used.
- the sorbent material comprises at least 70 wt% MOF of the invention, suitably at least 80%, suitably at least 95%. In a particular embodiment, the sorbent material consists of the MOF of the present invention.
- the present invention provides a method of manufacturing a compound of the first aspect, comprising associating an f-block metal ion (M) with a polydentate ligand (LIG), as defined herein.
- the method involves reacting a salt of the f-block metal ion (M) with a polydentate ligand (LIG), or suitable ionised form thereof.
- the salt of the f- block metal ion (M) is reacted with the polydentate ligand (LIG) (or a suitable ionised form thereof) with M in a stoichiometric excess of at least 1 .5:1 , suitably at least 1 .8:1 , suitably at least 2:1 , suitably to ensure that most or all of the ligand reacts.
- the f-block metal ion (M) and the polydentate ligand (LIG) are associated in the required stoichiometric proportions to yield a compound comprising species defined by the formula [M] x [LIG] y .
- the method comprises solvothermal combination of an f-block metal ion (M) salt with the polydentate ligand (LIG).
- Solvothermal syntheses are well known in the art.
- Solvothermal combination suitably involves heating the ingredients together in the presence of an organic solvent (suitably an alcohol, e.g. ethanol) optionally in the presence of water.
- Solvothermal combination suitably involves heating at a temperature between 70 and 150 ° C, suitably between 1 10 and 130 ° C under pressure such that at least some of the solvent is still liquid or supercritical fluid under the reaction conditions
- the method suitably comprises reacting a salt of the f-block metal ion (M) with a polydentate ligand (LIG) in a solvent system.
- the solvent system may comprise one or more solvents.
- the solvent system may comprise two or more solvents, most suitably two solvents.
- At least one of the solvents of the solvent system bears a lone pair of electrons capable of co-ordinating with the f-block metal ion (M).
- at least one of the solvents of the solvent system is a protic solvent.
- the solvent system suitably comprises an alcohol, most suitably ethanol.
- the solvent system may comprise water.
- the solvent system comprises ethanol and water.
- the ratio of ethanol to water in the solvent system is suitably between 10:1 and 1 :10 by volume, suitably between 5:1 and 1 :5 by volume, more suitably between 2:1 and 1 :2 by volume, most suitably 1 :1 by volume.
- the particular solvents and proportions thereof used in the reaction to form the MOF- compounds can have an important influence on the resulting 3-dimensional structure of the MOFs formed. For instance, the presence of water assists the reaction more generally, facilitating solubilisation amongst other things. However, the presence of an alcohol, especially ethanol, was found (especially where the f-block metal ion is cerium(lll)) to affect the final crystalline form of the MOF, in some cases mitigating against the formation of amorphous solids.
- the method may suitably involve separation of the MOF-compound from the solvent system. This may involve filtration of the MOF from the solvent system. In a particular embodiment, the MOF-compound is isolated directly from the reaction solvent system.
- the MOF-compound yielded may initially be a solvate.
- Such solvates can be important, as explained above, in determining the original 3D-crystal structure before solvates are optionally subsequently removed.
- the method may optionally involve an additional recrystallisation step, for instance, to furnish the correct MOF-solvate in the first instance.
- the method may also involve a drying and/or desolvation step.
- desolvation involves exposing the resulting MOF-compound to a temperature of 70 ° C or greater for a period of time suitable to obtain the desired form of the MOF-compound (whether partially desolvated or completely desolvated).
- desolvation involves exposure of the MOF-compound to temperatures of 95 ° C or greater, more suitably 150 ° C or greater, most suitably 250 ° C greater, for period of time suitable to attain the desired level of desolvation.
- Samples of the MOF-compound may be taken during the desolvation process and analysed (e.g. using crystallographic techniques) to determine whether or not desolvation should be ceased, for instance, to yield a desired partially desolvated compound.
- An aspect of the present invention provides an MOF-compound obtainable by, obtained by, or directly obtained by the method of manufacturing a compound described herein.
- the present invention provides a method of manufacturing a MOF, comprising providing the MOF-compound as defined herein in a solid form.
- the MOF is provided directly from the reaction to produce the MOF-compound, suitably directly from the reaction solvent system thereof.
- the MOF may be further treated and/or purified if deemed necessary.
- the MOF may be recrystallised in an appropriate solvent system, optionally the same as the reaction solvent system described hereinbefore. This may furnish the MOF as the appropriate solvate before it is then dried/desolvated as described hereinbefore.
- the MOF is completely desolvated before it is used.
- the present invention provides a method of manufacturing a sorbent material, comprising providing a MOF as defined herein optionally in admixture with one or more auxiliary sorbent substances and/or one or more carrier substances.
- the sorbent material may be merely the MOF itself, and as such is formed merely through the provision of the MOF.
- the MOF is further mixed with one or more auxiliary sorbent substances and/or one or more carrier substances.
- the sorbent material may additionally comprise silica, particularly porous silica.
- the sorbent material comprises the MOF associated (or attached to) a support, particularly a (porous) silica support.
- the MOF may be grown upon the support.
- a homogenous mixture is suitably formed through thorough mixing Method of Use of Compounds, MOFs, and Sorbent Materials of the Invention
- the present invention provides a use of an MOF-compound, an MOF, or an sorbent material as define herein for separating a desired component (e.g. p-xylene) from a mixture of components (e.g. mixture of xylenes).
- a desired component e.g. p-xylene
- a mixture of components e.g. mixture of xylenes
- the present invention provides a method of selectively sorbing a desired component from a mixture of components, the method comprising contacting the mixture of components with a sorbent material to selectively sorb the desired component within/to the sorbent material.
- the present invention provides a method of separating a desired component from a mixture of components, the method comprising:
- a desired component from a mixture of components by contacting the mixture of components with a sorbent material to selectively sorb the desired component within/to the sorbent material to produce a sorption complex (i.e. comprising the desired component sorbed into/to the sorbent material);
- the sorbent material may be activated, for example, by exposing to heat (e.g. a temperature of at least 70 ° C, or at least 95 ° C, or at least 150 ° C, or at least 250 ° C) for sufficient time to desolvate.
- heat e.g. a temperature of at least 70 ° C, or at least 95 ° C, or at least 150 ° C, or at least 250 ° C
- the MOF is selected from Ce(HTCPB), Ce(HTCPB) (H 2 0) 2 .75(EtOH)o.28 Ce(HTCPB)(H 2 0) 2 .75(EtOH)o.28, Ce(HTCPB)(H 2 0) 1 . 8 ., which are suitably used to separate p-xylene (the desired component) from a mixture of xylenes (suitably a mixture of p- /m-xylene at least).
- the mixture from which a desired component is sorbed is suitably a liquid mixture at standard ambient temperature and pressure (SATP), i.e. 25 ° C and 100 kPa.
- SATP standard ambient temperature and pressure
- the desired component is itself a liquid at SATP.
- the liquid mixture is a solution of the desired component.
- the mixture is (substantially) free from solvents (especially solvents with a boiling point less than 100 ° C).
- the mixture from which a desired component is sorbed is suitably a mixture of two or more components, i.e. a mixture of the desired component and at least one other component, suitably at least one other similar component.
- the mixture comprises the desired component and at least one other component which is an isomer of the desired component.
- the isomers are structural isomers (as opposed to stereoisomers).
- the mixture comprises the desired component and at least one other component which is structurally identical to the desired component, save for a different degree of saturation (i.e. the desired component may be unsaturated and the at least one other component saturated, and vice versa).
- the mixture comprises an aromatic desired component and at least one other aromatic component.
- the mixture comprises two or more benzene derivatives, suitably two or more different (1 -8C)dialkylbenzenes, one of which is the desired component.
- the mixture comprises p-xylene and m-xylene.
- p-xylene is the desired component.
- the mixture may additionally comprise other structural isomers of p-xylene.
- the mixture comprises propane and propene, one of which is the desired component.
- Sorption may include absorptions (within the bulk) and/or adsorption (at the surface).
- sorption is (predominantly) absorption.
- Selectively sorbing the desired component from the mixture of components involves contacting the mixture with a sorbent material for suitable time to allow the desired component to be selectively sorbed within/to the sorbent material.
- Contacting the mixture with the sorbent material may involve eluting the sorbent material with the mixture (e.g. such as in column chromatography).
- the sorbent material is a stationary phase, whilst the mixture is a mobile phase.
- the mixture is contact with a simulated moving bed of sorbent material and eluted accordingly.
- contacting may involve simple mixing of the mixture and sorbent material, optionally under agitate conditions. In a particular embodiment, there is no agitation.
- the relative loadings of sorbent material (particularly the total amount of MOF) and the mixture of components (particularly the desired component) are selected for optimal sorption selectivity.
- selectivity can be established by running a number of experiments at different loadings and examining the composition of sorbed product to determine which loading combination provides the optimal selectivity.
- the relative loadings are calculated with reference to the proportion of MOF in the sorbent material and the proportion of desired component in the substrate mixture.
- the weight ratio between the sorbent material and the mixture is from 1 :100 to 1 00:1 , suitably 1 :30 to 10:1 , suitably 1 :20 to 1 :1 .
- the weight ratio between the sorbent material and the mixture is between 1 :10 and 1 :9.
- the weight ratio between the MOF in the sorbent material and the desired component in the mixture is from 1 :50 to 50:1 , suitably 1 :15 to 5:1 , suitably 1 :10 to 2:1 .
- the weight ratio between the sorbent material and the mixture is between 1 :5 and 1 :4.
- Contact time is suitably at least 30 second, suitably at least 1 minute, more suitably at least 10 minutes, and optionally at least 24 hours. Contact time is suitably less than 14 days, suitably less than 8 days, and may be less than 48 hours.
- the sorption complex is a complex between the desired component and the sorbent material, especially the MOFs contained therein.
- the mother liquors remaining following sorption of the desired component may be separated from the sorption complex by methods well known in the art regarding separating solids from liquids.
- the method of separation comprises a form of filtration.
- the contacting step essentially involves eluting the sorbent material (stationary phase) with the mixture (mobile phase)
- the mother liquors may be simply allowed to drain from the sorbent material or otherwise be pumped away from the sorbent material or otherwise removed under suction. This is essentially a form of filtration, since the stationary phase remains in place whilst the liquid exits.
- the sorption complex is optionally washed, for example with a suitable solvent (e.g. that dissolves or is miscible with the mother liquors), to remove any excess mother liquors remaining associated with the sorption complex.
- a suitable solvent e.g. that dissolves or is miscible with the mother liquors
- dichloromethane or another suitable organic solvent may be used to wash the sorption complex.
- the sorption complex may be optionally dried further, for example, through suction drying.
- the sorption complex may be further treated to extract the desired component therefrom.
- Such treatments may involve chemical treatments (e.g. to break down the sorbent material to release the desired component) or physical treatments (e.g. high temperatures).
- the sorption complex is chemically treated to break down the MOF (i.e. through disintegrating the 3-dimensional structure of the MOF, for instance, by dissolving the polydentate ligand (LIG)) so as to release the desired component.
- LIG polydentate ligand
- the desired component is then suitably separated from the broken down MOF and any other components within the sorbent material, to isolate the desired component.
- the sorption complex is treated with aqueous base (e.g. aqueous sodium hydroxide) to break down the MOF (e.g. Ce(HTCPB) to release the desired component (e.g. p-xylene).
- MOF e.g. Ce(HTCPB)
- the resulting mixture is the optionally filtered (to remove any superfluous solids) before the desired component is separated from the aqueous phase.
- the desired component is a water-immiscible component such as a xylene
- this process is straight forward since xylene and the aqueous phase will be segregated at a phase boundary.
- Such water-immiscible components can be separated from the aqueous phase, and the aqueous phase optionally further washed with organic solvents to extract more of the desired component from the aqueous layer.
- the overall process of separating a desired component from a mixture of components suitably provides a "selectivity" for the desired component over undesired component(s) of greater than 4.5, suitably greater than 4.8.
- Selectivity is calculated by reference to the relevant GC traces, which produce a peak for pX and mX with a concentration assigned to it.
- a purified product comprising (or consisting of) the desired component obtainable by, obtained by, or directly obtained by the method of the eighth aspect.
- p-xylene obtainable by, obtained by, or directly obtained by the method of the eighth aspect.
- the MOF-compound is defined by:
- LIG being H 4 TCPB (or an ionised form thereof, especially the corresponding tricarboxylate tri-anion);
- the ratio x:y being between 0.9:1 and 1 .1 :1 .
- the MOF-compound is completely or substantially desolvated.
- the MOF-compound is for separating p-xylene from xylene mixtures.
- PXRD data was either collected in transmission geometry on station 11 1 , Diamond Light Source using synchrotron radiation at a wavelength of 0.825054 A (synchrotron XRD) or in transmission geometry in a capillary using a Cu Bruker D8 Advance Powder Diffractometer (lab XRD). Samples were rotated to minimise the effect of preferred orientation and hence improve the quality of the data.
- TGA was carried out using a SDT500 analyser using air as the carrier gas.
- C0 2 and CH 4 gas sorption isotherms were measured using the Intelligent Gravimetric Analyser (IGA) from Hiden. As made sample was washed with water and ethanol and left to air dry prior to use. A sample of 1 was outgassed at 100 °C under dynamic vacuum (10 ⁇ 5 mbar) until constant mass loss was reached. For the Brunauer- Emmett-Teller (BET) surface area measurement, the sample was cooled to 195 K by means of a Dewar vessel containing dry ice. The isotherm was measured to an absolute C0 2 pressure of 1 bar. For measurements at 273 K and 298 K, the sample was cooled using a Dewar vessel containing ice and water and water alone respectively. The samples in these cases were measured to a C0 2 pressure of 5 bar.
- IGA Intelligent Gravimetric Analyser
- GC measurements were carried out using a ZB-Wax capillary column. Solutions of 0.1 % (w/v) were prepared in DCM for injection into the GC. All separations were carried out using the following conditions: Carrier Gas, 50 KPa He; Column Temp Program, isothermal at 40 °C; Detector, 300 °C; Injector, 250 °C.
- the organic layer was washed with 1 M HCI (250 ml_), water (2 x 250 ml_), dried over MgS0 4 and filtered. The filtrate was concentrated on a rotary evaporator until approximately 50 ml_ of solvent remained. The suspension was diluted with 50 ml_ of acetone and filtered to afford 16.0 g of crude material. The solid was dissolved in hot toluene, a small amount of insoluble material was removed by filtration and the filtrate was concentrated to a volume of 50 ml. The suspension was allowed to cool to ambient temperature and the solid was collected by filtration.
- FIG. 1 shows two optical microscope images of Compound 1 at 1 1 .25x magnification.
- FIG. 2 shows four SEM images of crystallites of Compound 1.
- the solvothermal combination involves Ce(N0 3 ) 3 .6H 2 0 (20 mg) and H 4 TCPB (10 mg) added to EtOH (3 ml_) and H20 (3 ml_) in 12 mL borosillicate glass vial and the vials sealed. Heat at 2 ° C/min to 120 for 48 hours and cooled at 0.2 ° C/min back down to room temperature (25 ° C). At this stage the product was present in the mother liquor in the form of colourless single crystals which were separated from the mother liquor by vacuum filtration and washed with EtOH and H 2 0 to yield pure compound. Batches were also produced at 3x the scale (3x reagent in 3x solvent in 40 mL glass vial). These scaled-up batches were used in the selectivity tests below.
- Compound 1 is activated by heating at 100 °C under vacuum overnight yielding the desolvated Compound 2, which has the formula Ce(HTCPB).
- phase purity of as grown Compound 1 was confirmed by powder X-ray diffraction (Synchrotron XRD - see FIG. 3), thermogravimetric analysis (TGA - see FIG. 4), and CHN microanalysis (see Table 1 ).
- FIG. 4 shows a TGA profile of compound 1.
- a UV-visible spectrum shows absorption at 260 and 350 nm. Following excitation at 350 nm, 1 displays ligand based fluorescence which is quenched upon coordination to the metal, however no metal to ligand charge transfer is observed.
- Compound 1 is a 3D framework with 1 D porosity formed by channels running along the a-axis.
- the asymmetric unit contains one crystallographically unique Ce(lll) ion with a coordination number of 9 and one mono-protonated HTCPB ligand, leaving an overall neutral framework with the formula Ce(HTCPB)(H 2 0) 2 . 75 (EtOH)o. 2 8.
- the structure is based on isolated Ce 2 dimers which are held in a 3D structure by the HTCPB ligand.
- Each Ce 2 dimer is bridged by two Ce-O-C-O-Ce bidentate bridges and two Ce- ⁇ 2 - O-C-O-Ce tridentate bridges, filling five of the nine sites in the coordination sphere of Ce.
- Two monodentate carboxylates are also coordinated each Ce, one protonated and one non-protonated at the axial positions of the Ce 2 dimer.
- the final two sites in the coordination sphere are filled by coordination of one H 2 0 and one EtOH atom to each Ce, oriented into the channels.
- the IR of 1 shows that there are three carboxylate bonding environments within the material.
- the framework can be penetrated by a spherical probe radius of 1 .4 A, 0.9 A and 0.5 A down the a, b and c-axes respectively, with the largest spherical void being 4.4 A in diameter, giving a packing index of 54.26 %.
- Compound 2 is the desolvated form of compound 1 , in which both channel solvent and coordinated H 2 0 and EtOH molecules have been removed from each Ce centre. This allows for the formation of a bidentate carboxylate bridge between the Ce 2 dimers forming Ce- carboxylate chains propagating parallel to the c-axis. This change does not affect the dimensionality as it remains a 3D framework, but the carboxylate bridge forming where EtOH and H 2 0 have been removed from the Ce centres takes overall coordination number down from 9 to 8.
- the framework can be penetrated by a spherical probe radius of 2.1 A, 0.6 A and 0.3 A down the a, b and c-axes respectively, with the largest spherical void being 4.6 A in diameter with a packing index of 56.17 %.
- Compound 2 has two distinct channels present.
- the 'blue' channel is the smaller of the two channels and is square in shape. It lies between the 1 -/2- and 4-/5- positions of the central aromatic ring of the HTCPB ligand, with the pendent carboxyphenyl groups leading to Ce lining the channels.
- the inversion centre in the middle of the channel and within the blue channel, the protonated 017-C16-018(-H) carboxylate unit is present.
- the larger 'green' channel lies between the 2-/4- and 5-/1 - positions of the same central aromatic ring of the HTCPB ligand.
- the carboxyphenyl groups also line the channels, however due to the larger distance between the pendent groups, the channel is more rectangular in shape.
- the inversion centre again is at the centre of the channel, meaning both channels are symmetrical, but due to their position with respect to the ligand, the blue channel is square and the green is rectangular.
- the channel solvent is coloured depending on the channel name assignments; H 2 0 is found in the blue channel and EtOH is found in the green channel of 1.
- the total solvent accessible volume of 2 is 405 A 3 , corresponding to 24.9 % of the total volume of the unit cell calculated using Olex2. This can be broken down into the two channels: The blue channel is responsible for 1 1 .4 % of this void space with a volume of 186.2 A 3 per unit cell. The green channel accounts for the remaining 13.5 % of the void space, with a volume of 218.8 A 3 .
- FIG. 6 shows (a) an N 2 isotherm of compound 2 collected at 77 K; and (b) an H 2 0 isotherm of compound 2 collected at 295 K following activation 1 at 100 °C at 10 "5 mbar overnight.
- FIG. 7 shows (a) a C0 2 isotherm of compound 2 collected at 195 K following activation 1 at 1 00 °C at 1 0 ⁇ 5 mbar overnight; (b) a BET plot for surface area determination; and (c) a Dubnin-Raduschevich plot for calculation of pore volume based on 1 95 K isotherm.
- FIG. 8 relates to Isosteric Heat (Q st ) Determination of compound 2 and shows (a) C0 2 and CH 4 isotherms collected at 273 K and 298 K; and (b) C0 2 and CH 4 Q st .
- a type I isotherm shows that 2 is permanently porous to H 2 0 at 295 K and 25 mbar (FIG. 6(b)).
- the framework is structurally stable following isotherm measurement. It is also stable to immersion in water and subsequent guest removal.
- a reversible type 1 isotherm shows that 2 is permanently porous to C0 2 at 195 K and 1 bar (FIG. 7(a)).
- the C0 2 isotherm is type I, characteristic of microporous materials 20 .
- the Dubinin- Radushkevich 21 (DR) pore volume of 2 calculated from the C0 2 adsorption branch is 0.198 cm 3 g "1 compared with a pore volume of 0.208 cm 3 g "1 of the rigid host structure from single crystal data (FIG. 7(c)).
- a step isotherm shows that 2 is permanently porous to N 2 at 77 K and 1 bar (FIG. 6(a)).
- the isotherm shows a step in adsorption between 50 and 200 mbar which is also apparent in the curve desorption over the same range, however the some hysteresis is seen in the desorption. These factors suggest there may be a phase change with adsorption of N 2 .
- the pore size distribution was calculated by means of an Ar isotherm at standard temperature and pressure, which showed a maximum pore size of 10 A. This is in good agreement with the pore distances measured from the single crystal structure in which the the smaller of two channels is approximately 8.9 x 7.9 A and the larger is 7.0 x 10.4 A.
- C0 2 and CH 4 isotherms were also collected for 2 at 273 K and 298 K (FIG. 8(a)).
- Isosteric heats of adsorption, Q st , for C0 2 and CH 4 were derived from a virial-type expression fitted to the adsorption branches of the isotherms measured at 273 K and 298 K (FIG. 8(b)).
- the strength of interaction between 2 and the C0 2 increases from 18 kJmol "1 at zero coverage to 22 kJmol "1 at high loading.
- the interaction between 2 and CH 4 decreases from 21 .5 kJmol "1 at zero coverage to 1 8 kJmol "1 at high loading.
- GCMC Grand Canonical Monte Carlo
- FIG. 9 shows TGA profiles of loaded 2 with pX and mX individually.
- FIG. 10 shows (a) Powder x-ray diffraction profiles of loaded material following xylene uptake experiments on compound 2; and (b) TGA profiles of loaded material following xylene uptake experiments on compound 2.
- Table 4 Selectivity of 2 towards mixtures of pX, mX, oX and EB.
- Ce(HTCPB)- (pXoX) o.75(DCM) 0 . 13 (H 2 0)o.io Calc C: 61 .16 H : 3.45 Observed C: 61 .13 H: 3.39 TGA mass loss expected 1 1 .73% found 12.04%
- Ce(HTCPB)- (mXEB) o.55(DCM)o.i5(H 2 0)o.23 Calc C: 60.06 H: 3.30 Observed C: 60.06 H: 3.31 TGA mass loss expected 9.76% found 9.18%
- FIG. 1 1 shows analysis of the relative amounts of compound 2 (red) and xylene loaded compound 2PM (blue) over the time course of the pXmX selectivity experiments.
- Phase 2 is still present at around 30 % after 1 minute alongside a 'loaded' phase, 2PM, which has a larger unit cell volume than 2. After 10 minutes, the amount of 2 has reduced to 20 % and has completely disappeared by 24 hours. The unit cell volume of 2 increases slightly between 1 and 1 0 minutes due to loading of the material before conversion to 2PM. Phase 2PM is present at all times throughout the experiment, however the unit cell volume is decreasing with time. This may be due to ordering of the xylene molecules within the channels; initially at 1 minute there is a large amount of disorder so the structure has a larger unit cell volume, but as the xylenes become more ordered and form interactions with the channel walls, the unit cell volume decreases (FIG. 1 1 ).
- Structure analysis of 2P shows that the core structure is the same as 2 but with a larger unit cell volume due to the inclusion of pX into the framework; 2 has a unit cell volume of 1632.08 A 3 , which increases to 1673.27 A 3 in 2P.
- Analysis of the void space in 2P with xylenes removed give a total accessible volume of 448.9 A 3 , corresponding to 26.8 % of the unit cell volume (compared to 405 A 3 and 24.9 % respectively in 2).
- Analysis of the blue and green channels individually show increases in the size of both from 2, with the blue channel now being 206.4 and the green being 242.5 A 3 compared to 186.2 A 3 and 218.8 A 3 respectively in 2.
- Phase 2 is still present at around 30 % after 1 minute alongside a 'loaded' phase, 2PM, which has a larger unit cell volume than 2. After 10 minutes, the amount of 2 has reduced to 20 % and has completely disappeared by 24 hours. The unit cell volume of 2 increases slightly between 1 and 10 minutes due to loading of the material before conversion to 2PM. Phase 2PM is present at all times throughout the experiment, however the unit cell volume is decreasing with time.
- the single crystal structure of 2M again has the same structure as 2, but it has an even larger unit cell volume than both 2 and 2P of 1729.02 A 3 .
- Analysis of the void space in 2M with xylenes removed give a total accessible volume of 501 .8 A 3 , corresponding to 29.0 % of the unit cell volume (compared to 405 A 3 and 24.9 % respectively in 2 and 448.9 and 24.9 % respectively in 2P ).
- Analysis of the blue and green channels individually show increases in the size of both from 2 and 2P, with the blue channel now being 218.2 A 3 and the green being 283.6 A 3 compared to 186.2 A 3 and 218.8 A 3 respectively in 2 and 206.4 A 3 and 242.5 A 3 respectively in 2P).
- the framework has had to distort to a greater extent in the case of 2M due to the inclusion of the larger mX and its disordered presence within both channels.
- the molecule In the blue channel, the molecule is disordered about the central aromatic ring, and occupies a total volume of 125 A 3 at isolated 'pinch points' along the 1 D channel.
- mX In the green channel, mX is disordered over two positions across an inversion centre occupying 135 A 3 , and the whole disordered molecule is disordered throughout the length of the channel.
- the relative occupancies of both mX molecules are 1 00 % and 50 % in the blue and green channels respectively giving an average amount of 75% mX per formula unit (compared to 100 % occupancy of pX in 2P).
- Table 7 shows the xylene selectivity performance of cerium MOFs of the invention as compared to MOFs of the prior art.
- the cerium species of Table 8 is similar to that described in Example 1 , only with different crystallite sizes.
- the Ce(HTCPB) of Example 1 was produced as a pure phase but in microcrystalline form, with particle sizes ranging from 2-20 ⁇ , via the 3x scaled— up process described in Example 1 ..
- the Ce(HTCPB) used in table 8 was synthesised using the non-scaled- up process of Example 1 , in which large single crystals with a particle size around 50 ⁇ were produced.
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GB201215693D0 (en) * | 2012-09-03 | 2012-10-17 | Univ Liverpool | Metal-organic framework |
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US10273209B2 (en) * | 2014-05-26 | 2019-04-30 | King Abdullah University Of Science And Technology | Design, synthesis and characterization of metal organic frameworks |
CN104275154B (en) * | 2014-10-16 | 2016-06-01 | 东南大学 | A kind of matrix material and its preparation method that can be separated Mixed XYLENE |
JP2017014146A (en) * | 2015-06-30 | 2017-01-19 | 学校法人 関西大学 | Method for separating paraxylene using metal organic structure |
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WO2017060856A1 (en) * | 2015-10-06 | 2017-04-13 | King Abdullah University Of Science And Technology | A rare earth-based metal-organic framework for moisture removal and control in confined spaces |
CN105363416B (en) * | 2015-12-07 | 2018-02-23 | 中国科学院生态环境研究中心 | Manganese dioxide nanowire@multidimensional mesoporous metal organic framework sorbents and its preparation |
KR102011393B1 (en) * | 2016-10-17 | 2019-08-16 | 한국화학연구원 | Adsorbents for the separation of olefin-paraffin mixtures including C2-C4 hydrocarbons and a separation method of olefin-paraffin gas mixtures using the same |
CN106582540B (en) * | 2016-12-20 | 2019-08-30 | 安徽大学 | Metal organic framework and preparation and as the application of defluorinating agent based on rare earth element ion implantation |
CN107812539A (en) * | 2017-11-14 | 2018-03-20 | 江苏师范大学 | A kind of methanol alkylation produces the preparation method of paraxylene catalyst |
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CN109569026B (en) * | 2018-01-11 | 2021-12-03 | 南开大学 | Preparation of chromatographic stationary phase with porous frame material as matrix for chiral separation |
CN110961080B (en) * | 2018-09-29 | 2022-06-28 | 中国石油化工股份有限公司 | Adsorption separation C8Adsorbent for aromatic hydrocarbon and preparation method thereof |
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CN110172159B (en) * | 2019-06-04 | 2020-01-21 | 东莞东阳光科研发有限公司 | Ln-MOFs nanosphere and preparation method and application thereof |
CN111410596B (en) * | 2020-04-02 | 2021-03-30 | 浙江大学 | Separation method of carbon octa-aromatic hydrocarbon isomer mixture |
CN112604660A (en) * | 2020-11-27 | 2021-04-06 | 华侨大学 | Preparation method and application of Ce-MOFs phosphorus removal adsorbent |
CN112973638B (en) * | 2021-02-23 | 2023-03-28 | 云南省水利水电科学研究院 | Preparation method and application of modified MIL-125 (Ti) material for removing micro-polluted mercury in water body |
CN114106346B (en) * | 2021-10-29 | 2023-04-18 | 重庆第二师范学院 | Rare earth bimetallic electrochemiluminescence material and preparation method and application thereof |
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CN114452945A (en) * | 2022-02-15 | 2022-05-10 | 中国船舶重工集团公司第七一九研究所 | Preparation method of MOF composite material adsorbent for removing toluene gas |
CN114573826B (en) * | 2022-02-28 | 2022-12-27 | 上海交通大学 | Two-dimensional metal organic framework based on isocyano coordination, preparation method and application |
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WO2015171791A1 (en) * | 2014-05-06 | 2015-11-12 | Massachusetts Institute Of Technology | Compositions and methods comprising conductive metal organic frameworks and uses thereof |
US10118877B2 (en) * | 2014-12-03 | 2018-11-06 | The Regents Of The University Of California | Metal-organic frameworks for aromatic hydrocarbon separations |
US10413858B2 (en) * | 2015-12-28 | 2019-09-17 | Arizona Board Of Regents On Behalf Of Arizona State University | Metal-organic framework-based sorbents and methods of synthesis thereof |
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US9981243B2 (en) | 2018-05-29 |
CN104918672B (en) | 2017-04-05 |
US20150231600A1 (en) | 2015-08-20 |
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